title: Spin-driven activation of dioxygen in various metalloenzymes and their inspired models.
abstract: Although potentially powerful, molecular oxygen is an inert oxidant due to the triplet nature of its ground state. Therefore, many enzymesse various metal cations (M) to produce singlet active species M(n) O(2) . In this communication we investigate the topology of the Electron Localization Function (ELF) within five biomimetic complexes which are representative of the strategies followed by metalloenzymes to activate O(2) . Thanks to its coupling to the constrained DFT methods the ELF analysis reveals the tight connection between the spin state of the adduct and the spatial organization of the oxygen lone pairs. We suggest that enzymes could resort to spin state control to tune the regioselectivity of substrate oxidations.
authors.affiliation: Department of Chemistry and Institute for Biocomplexity and Informatics, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4. aurelien.de-la-lande@u-psud.fr
authors.forename: Aurelien
authors.initials: A
authors.lastname: de la Lande
authors.forename: Dennis R
authors.initials: DR
authors.lastname: Salahub
authors.forename: Jacques
authors.initials: J
authors.lastname: Maddaluno
authors.forename: Anthony
authors.initials: A
authors.lastname: Scemama
authors.forename: Julien
authors.initials: J
authors.lastname: Pilme
authors.forename: Olivier
authors.initials: O
authors.lastname: Parisel
authors.forename: Helene
authors.initials: H
authors.lastname: Gerard
authors.forename: Michel
authors.initials: M
authors.lastname: Caffarel
authors.forename: Jean-Philip
authors.initials: JP
authors.lastname: Piquemal
mesh_terms: D008667:Metalloproteins / Q000737:chemistry / Q000378:metabolism*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry / Q000378:metabolism*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D008667:Metalloproteins; D010100:Oxygen